CN107663249B - Catalyst composition for long-chain alpha-olefin polymerization and method for catalyzing long-chain alpha-olefin polymerization by using catalyst composition - Google Patents
Catalyst composition for long-chain alpha-olefin polymerization and method for catalyzing long-chain alpha-olefin polymerization by using catalyst composition Download PDFInfo
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Abstract
The invention provides a catalyst composition for long-chain α -olefin polymerization and a method for catalyzing long-chain α -olefin polymerization by using the catalyst composition1‑R5The same or different, each independently selected from hydrogen, halogen, C1‑C20And C is a hydrocarbon group4‑C10The method for catalyzing the polymerization of the long-chain α -olefin comprises the step of contacting the long-chain α -olefin, a main catalyst, a cocatalyst and a chain transfer agent to carry out polymerization reaction in the presence of inert gas, wherein the catalyst composition has high catalytic activity and good thermal stability when catalyzing α -olefin chain transfer polymerization, and is used for synthesizing the poly α -olefin with controllable molecular weight.
Description
Technical Field
The invention relates to the technical field of catalysts for olefin polymerization, and in particular relates to a catalyst composition for long-chain alpha-olefin chain transfer polymerization and a method for catalyzing long-chain alpha-olefin polymerization by using the catalyst composition.
Background
Poly-alpha-olefin synthetic oil (PAO) is an oil product with high purity produced by alpha-olefin through oligomerization and hydrogenation saturation under the action of a catalyst. Compared with mineral oil, PAO has the characteristics of high viscosity index, low pour point, high flash point, excellent high and low temperature performance and the like, and can not be replaced in many oil products. A significant challenge in the preparation of alpha-olefin synthetic oils is the search for a method of controlling the viscosity index of the polyalphaolefins, i.e., controlling the molecular weight and distribution of the polyalphaolefins.
The single-site polyolefin catalyst can well control the microstructure of the synthesized polyolefin molecules, particularly can realize the active polymerization of the olefin molecules under certain conditions, and in the active polymerization of the polyolefin, each catalyst can only enable one polymer chain to carry out the polymerization propagation reaction, thereby precisely controlling the chemical structure, the molecular weight and the molecular weight distribution of the polyolefin molecules. In order to significantly reduce the consumption of the more expensive transition metals in the catalyst component, allowing the synthesis of multiple polyolefin molecules per catalyst molecule, researchers have developed coordination chain transfer polymerization of olefins. The coordination chain transfer polymerization of the olefin can realize the controllable/active chain growth process of polyolefin molecules and can realize the design and control of the polyolefin molecular structure. Recent studies at home and abroad find that chain transfer agents (CSA) (generally alkyl metal compounds such as aluminum alkyl, zinc alkyl and the like) are used for catalyzing ethylene polymerization by using a single-active-site catalyst, and have a plurality of advantages.
Patent document CN103288985A provides a α -diimine nickel metal complex (chemical structure is shown as formula (II)) for catalyzing ethylene, propylene and C6-C18The α -olefin homopolymerization or copolymerization reaction is carried out, but the molecular weight of the obtained polymer is higher and is about 200000-400000, so that the wide application of the polymer in PAO is influenced.
Patent document CN105482000A provides a catalyst for olefin polymerization, wherein the main catalyst can catalyze ethylene homopolymerization or copolymerization reaction at high temperature with high activity, but when the catalyst is used for catalyzing long-chain α -olefin polymerization, the molecular weight of the obtained polymer is high, which affects the wide application of the catalyst in PAO.
Disclosure of Invention
The invention aims to provide a catalyst composition capable of catalyzing long-chain alpha-olefin chain polymerization at a higher temperature and a method for catalyzing long-chain alpha-olefin polymerization by using the catalyst composition, aiming at the technical defects of poor thermal stability, high molecular weight of long-chain alpha-olefin catalysis and the like of the existing alpha-diimine nickel metal catalyst; the catalyst composition has high catalytic activity and good thermal stability when catalyzing the chain transfer polymerization of alpha-olefin, and is used for synthesizing poly alpha-olefin with controllable molecular weight.
In order to achieve the above objects, the present invention provides a catalyst composition for polymerization of long chain α -olefins, comprising the following components:
a main catalyst, a cocatalyst and a chain transfer agent;
the main catalyst is a complex with a chemical structure shown as a formula (I):
wherein X is halogen; r1-R5The same or different, each independently selected from hydrogen, halogen, C1-C20And C is a hydrocarbon group4-C10At least one of heterocyclic groups;
the cocatalyst is selected from at least one of alkyl aluminoxane, aryl boron and borate;
the chain transfer agent is selected from trialkyl aluminum and/or dialkyl zinc.
In the present invention, the alkyl group includes, but is not limited to, alkyl, alkenyl, alkynyl, aryl.
According to the catalyst composition provided by the invention, preferably, in the formula (I), R1-R5Each independently selected from hydrogen, halogen, C1-C13And C is a hydrocarbon group4-C8At least one of heterocyclic groups. Further preferably, R1-R5Each independently selected from hydrogen, fluorine, chlorine, bromine, methyl, ethyl, ethenyl, isopropyl, propenyl, phenyl, C7-C13At least one of aralkyl, furyl, pyrrolyl, thienyl and pyridyl.
According to the catalyst composition provided by the present invention, preferably, the complex is selected from at least one of the following compounds:
1) a complex of formula (I), wherein R1＝R3＝R5＝H，R2＝R4Me, X ═ Br (complex 1 for short, the same applies below);
2) a complex of formula (I), wherein R1＝R3＝R2＝R4＝Me，R5＝H，X＝Br；
3) A complex of formula (I), wherein R1＝R3＝R5＝H，R2＝R4＝iPr，X＝Br；
4) A complex of formula (I), wherein R1＝R3＝R5＝H，R2＝R4＝CHPh2，X＝Br；
5) A complex of formula (I), wherein R1＝R3＝H，R2＝R4＝R5＝CHPh2，X＝Br；
6) A complex of formula (I), wherein R1＝R3＝R2＝R4＝R5＝CHPh2，X＝Br；
7) A complex of formula (I), wherein R1＝R3＝R5＝H，R2＝R4＝Me，X＝Cl；
8) A complex of formula (I), wherein R1＝R3＝R2＝R4＝Me，R5＝H，X＝Cl；
9) A complex of formula (I), wherein R1＝R3＝R5＝H，R2＝R4＝iPr，X＝Cl；
10) A complex of formula (I), wherein R1＝R3＝R5＝H，R2＝R4＝CHPh2，X＝Cl；
11) A complex of formula (I), wherein R1＝R3＝H，R2＝R4＝R5＝CHPh2，X＝Cl；
12) A complex of formula (I), wherein R1＝R3＝R2＝R4＝R5＝CHPh2，X＝Cl。
According to the catalyst composition provided by the present invention, preferably, the alkylaluminoxane is methylaluminoxane and/or modified methylaluminoxane; the aryl boron is phenyl boron, preferably trifluorophenylboron; the borate is N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.
According to the catalyst composition provided by the invention, preferably, the chain transfer agent is selected from at least one of trimethyl aluminum, triethyl aluminum, triisopropyl aluminum, triisobutyl aluminum, tri-n-hexyl aluminum, tri-n-octyl aluminum, dimethyl zinc and diethyl zinc.
According to the catalyst composition provided by the invention, preferably, the molar ratio of the aluminum in the cocatalyst to the nickel in the main catalyst is (10-10000): 1; or the molar ratio of boron in the cocatalyst to nickel in the main catalyst is (1-500): 1.
According to the catalyst composition provided by the invention, preferably, the molar ratio of aluminum in the chain transfer agent to nickel in the main catalyst is (1-1000):1, more preferably (5-500): 1; or the molar ratio of zinc in the chain transfer agent to nickel in the main catalyst is (1-1000):1, more preferably (3-500): 1.
The invention also provides a method for catalyzing the polymerization of long-chain alpha-olefin by the catalyst composition, which comprises the following steps: in the presence of inert gas, the long-chain alpha-olefin, the main catalyst, the cocatalyst and the chain transfer agent are contacted to carry out polymerization reaction.
According to the method provided by the invention, the polymerization reaction temperature is preferably-78-200 ℃, preferably-20-150 ℃, and further preferably 30-120 ℃.
The long-chain α -olefin is aliphatic terminal olefin with the carbon number of more than or equal to 5, and the method is particularly suitable for C6-C18α -olefin of (1).
According to the method provided by the invention, preferably, the amount of the main catalyst in the long-chain alpha-olefin polymerization is 0.0001-10 mmol/L; further preferably 0.001 to 1 mmol/L.
Compared with the prior art, the invention has the following beneficial effects:
when the invention is used for carrying out alpha-olefin chain transfer polymerization reaction, the catalyst composition still maintains higher catalytic activity at 100 ℃; the molecular weight of the obtained polymer can be controlled by selecting and adding the chain transfer agent, so that the molecular weight of the obtained product is reduced, and the quality of the poly alpha-olefin product is improved; more importantly, the catalyst composition is used for carrying out bulk polymerization catalysis reaction, which has very important significance for industrial production of poly alpha-olefin.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below by way of examples, however, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
Example 1
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 7.3mg (10. mu. mol) of complex 1, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 0.5ml of diethylzinc (1.0mol/l in toluene) were added in this order, and polymerization was stopped after 2 hours at 100 ℃ to make the reaction system black and sticky. Diluting with hydrochloric acid-ethanolThe reaction was terminated, the resulting polymer was dissolved in tetrahydrofuran, precipitated with methanol, and repeated three times, and finally the sample was dried in a vacuum oven for 24 hours to obtain 2.12g of a polymer having a certain elasticity and being in a white solid form. The catalytic efficiency of the catalytic system was 212kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 28.32 ten thousand, and molecular weight distribution Mw/Mn was 2.21.
Comparative example 1:
a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 7.3mg (10. mu. mol) of complex 1, 15ml of 1-decene, and 0.8ml of Methylaluminoxane (MAO) (1.53mol/l toluene solution) were sequentially added thereto, and polymerization was stopped after 2 hours at 100 ℃ to obtain a black and viscous reaction system. The reaction was terminated with a dilute hydrochloric acid-ethanol solution, the resulting polymer was dissolved in tetrahydrofuran, precipitated with methanol, and repeated three times, and finally the sample was placed in a vacuum oven and dried for 24 hours to give 3.22g of a polymer in the form of a white solid with a certain elasticity. The weight average molecular weight of the polymer was measured at the end of the reaction and was 38.74 ten thousand, and the molecular weight distribution Mw/Mn was 2.23.
Comparative example 2:
a100 ml three-necked reaction flask was evacuated, and replaced with nitrogen three times, and 7.2mg (10. mu. mol) of comparative complex 1 (structural formula (II)), 15ml of 1-decene, and 0.8ml of Methylaluminoxane (MAO) (1.53mol/l toluene solution) were sequentially added thereto, and polymerization was stopped after 2 hours at 90 ℃ to obtain a black and viscous reaction system. The reaction is stopped by dilute hydrochloric acid-ethanol solution, the obtained polymer is dissolved by tetrahydrofuran, methanol is precipitated, the steps are repeated for three times, and finally, the sample is placed into a vacuum drying oven to be dried for 24 hours, so that 0.52g of white solid polymer with certain elasticity is obtained. The catalytic efficiency of the catalytic system was 52kg mol-1Ni。
Comparative example 3:
a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 7.2mg (10. mu. mol) of comparative complex 1 (structure) was added in this orderAs shown in the formula (II), 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene), 0.5ml of diethylzinc (1.0mol/l in toluene) were polymerized at 90 ℃ for 2 hours, and the polymerization was stopped, and the reaction system was black and viscous. The reaction is stopped by dilute hydrochloric acid-ethanol solution, the obtained polymer is dissolved by tetrahydrofuran, methanol is precipitated, the reaction is repeated for three times, and finally, the sample is placed into a vacuum drying oven to be dried for 24 hours, so that 0.38g of white solid polymer with certain elasticity is obtained. The catalytic efficiency of the catalytic system was 38kg mol-1Ni。
Example 2
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 7.3mg (10. mu. mol) of complex 1, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 1.0ml of diethyl zinc (1.0mol/l in toluene) were added in this order, and polymerization was stopped after 2 hours at 100 ℃ to make the reaction system black and sticky. The reaction is stopped by dilute hydrochloric acid-ethanol solution, the obtained polymer is dissolved by tetrahydrofuran, methanol is precipitated, the reaction is repeated for three times, and finally the sample is placed into a vacuum drying oven to be dried for 24 hours, so that 1.64g of white solid polymer with certain elasticity is obtained. The catalytic efficiency of the catalytic system was 164kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 15.24 ten thousand, and molecular weight distribution Mw/Mn was 1.88.
Example 3
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 7.3mg (10. mu. mol) of complex 1, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 2.0ml of diethylzinc (1.0mol/l in toluene) were added in this order, and polymerization was stopped after 2 hours at 100 ℃ to make the reaction system black and sticky. The reaction is stopped by dilute hydrochloric acid-ethanol solution, the obtained polymer is dissolved by tetrahydrofuran, methanol is precipitated, the steps are repeated for three times, and finally the sample is placed into a vacuum drying oven to be dried for 24 hours, so that 1.12g of polymer with certain elasticity is obtained. The catalytic efficiency of the catalytic system was 112kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 8.27 ten thousand, and molecular weight distribution Mw/Mn was 2.06.
Example 4
A100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 7.3mg (10. mu. mol) of complex 1, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 1.0ml of trimethylaluminum (1.0mol/l in toluene) were sequentially added thereto, and polymerization was stopped after 2 hours at 100 ℃ to obtain a black and viscous reaction system. The reaction is stopped by dilute hydrochloric acid-ethanol solution, the obtained polymer is dissolved by tetrahydrofuran, methanol is precipitated, the reaction is repeated for three times, and finally, the sample is placed into a vacuum drying oven to be dried for 24 hours, so that 0.64g of white solid polymer with certain elasticity is obtained. The catalytic efficiency of the catalytic system was 64kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 2.01 ten thousand, and molecular weight distribution Mw/Mn was 2.17.
Example 5:
a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 13.7mg (10. mu. mol) of complex 5, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 2.0ml of diethylzinc (1.0mol/l in toluene) were added in this order, and polymerization was stopped after 2 hours at 100 ℃ to make the reaction system black and sticky. The reaction was terminated with a dilute hydrochloric acid-ethanol solution, the resulting polymer was dissolved in tetrahydrofuran, precipitated with methanol, and repeated three times, and finally the sample was placed in a vacuum oven and dried for 24 hours to give 5.14g of a polymer having a certain elasticity and being a white solid. The catalytic efficiency of the catalytic system was 514kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 28.14 ten thousand, and molecular weight distribution Mw/Mn was 1.92.
Example 6:
a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 6.4mg (10. mu. mol) of complex 7, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 1.0ml of diethylzinc (1.0mol/l in toluene) were added in this order, and polymerization was stopped after 2 hours at 100 ℃ to make the reaction system black and sticky. Terminating the reaction with dilute hydrochloric acid-ethanol solution, washing the obtained polymer with acetone, and drying the sample in a vacuum drying oven for 24 hr to obtain 1.47g white solid with oneA polymer of fixed elasticity. The catalytic efficiency of the catalytic system was 147kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 13.28 ten thousand, and molecular weight distribution Mw/Mn was 1.92.
Example 7:
a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 6.4mg (10. mu. mol) of complex 7, 15ml of 1-decene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 2.0ml of diethylzinc (1.0mol/l in toluene) were sequentially added thereto, and polymerization was stopped after 2 hours at 100 ℃ to obtain a black and viscous reaction system. The reaction was terminated with dilute hydrochloric acid-ethanol solution, the resulting polymer was washed with acetone, and finally the sample was dried in a vacuum oven for 24 hours to give 0.82g of polymer. The catalytic efficiency of the catalytic system was 82kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 7.95 ten thousand, and molecular weight distribution Mw/Mn was 2.04.
Example 8:
a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 7.3mg (10. mu. mol) of complex 1, 15ml of 1-dodecene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l toluene solution) and 1.0ml of diethyl zinc (1.0mol/l toluene solution) were sequentially added thereto, and polymerization was stopped after 2 hours at 100 ℃ to obtain a black and viscous reaction system. The reaction was terminated with a dilute hydrochloric acid-ethanol solution, the resulting polymer was dissolved in tetrahydrofuran, precipitated with methanol, and repeated three times, and finally the sample was dried in a vacuum oven for 24 hours to give 1.92g of a polymer having a certain elasticity and being in the form of a white solid. The catalytic efficiency of the catalytic system was 192kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 18.07 ten thousand, and molecular weight distribution Mw/Mn was 1.98.
Example 9:
a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 7.3mg (10. mu. mol) of complex 1, 15ml of 1-dodecene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l toluene solution) and 2.0ml of diethyl zinc (1.0mol/l toluene solution) were sequentially added thereto, and polymerization was stopped after 2 hours at 100 ℃ to obtain a black and viscous reaction system. Using dilute hydrochloric acid-ethanol solutionThe reaction was terminated, the resulting polymer was dissolved in tetrahydrofuran, methanol precipitated, and the procedure was repeated three times, and finally the sample was dried in a vacuum oven for 24 hours to obtain 0.92g of a polymer with a certain elasticity. The catalytic efficiency of the catalytic system was 92kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 9.33 ten thousand, and molecular weight distribution Mw/Mn was 1.87.
Example 10:
a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 7.3mg (10. mu. mol) of complex 1, 15ml of 1-tetradecene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l toluene solution), and 1.0ml of diethylzinc (1.0mol/l toluene solution) were sequentially added thereto, and polymerization was stopped after 2 hours at 100 ℃ to obtain a black and viscous reaction system. The reaction is stopped by dilute hydrochloric acid-ethanol solution, the obtained polymer is dissolved by tetrahydrofuran, methanol is precipitated, the reaction is repeated for three times, and finally, the sample is placed into a vacuum drying oven to be dried for 24 hours, so that 2.03g of white solid polymer with certain elasticity is obtained. The catalytic efficiency of the catalytic system was 203kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 21.21 ten thousand, and molecular weight distribution Mw/Mn was 2.12.
Example 11:
a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 7.3mg (10. mu. mol) of complex 1, 15ml of 1-tetradecene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l toluene solution) and 2.0ml of diethylzinc (1.0mol/l toluene solution) were sequentially added thereto, and polymerization was stopped after 2 hours at 100 ℃ to obtain a black and viscous reaction system. The reaction was terminated with a dilute hydrochloric acid-ethanol solution, the resulting polymer was dissolved in tetrahydrofuran, precipitated with methanol, and repeated three times, and finally the sample was placed in a vacuum oven and dried for 24 hours to give 1.46g of a polymer having a certain elasticity and being a white solid. The catalytic efficiency of the catalytic system was 146kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 13.24 ten thousand, and molecular weight distribution Mw/Mn was 1.97.
Example 12:
a100 ml three-neck reaction flask was evacuated, replaced with nitrogen three times, and 7.3 portions were added in sequencemg (10. mu. mol) of complex 1, 15ml of 1-hexadecene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene), 1.0ml of diethylzinc (1.0mol/l in toluene) were polymerized at 100 ℃ for 2 hours and then stopped, and the reaction was black and sticky. The reaction was terminated with a dilute hydrochloric acid-ethanol solution, the resulting polymer was dissolved in tetrahydrofuran, precipitated with methanol, and repeated three times, and finally the sample was placed in a vacuum oven and dried for 24 hours to give 2.27g of a polymer in the form of a white solid with a certain elasticity. The catalytic efficiency of the catalytic system was 227kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 21.96 ten thousand, and molecular weight distribution Mw/Mn was 2.18.
Example 13:
a100 ml three-necked reaction flask was evacuated and replaced with nitrogen three times, and 7.3mg (10. mu. mol) of complex 1, 15ml of 1-hexadecene, 0.8ml of Methylaluminoxane (MAO) (1.53mol/l in toluene) and 2.0ml of diethylzinc (1.0mol/l in toluene) were sequentially added thereto, and polymerization was stopped after 2 hours at 100 ℃ to obtain a black and viscous reaction system. The reaction is stopped by dilute hydrochloric acid-ethanol solution, the obtained polymer is dissolved by tetrahydrofuran, methanol is precipitated, the steps are repeated for three times, and finally the sample is placed into a vacuum drying oven to be dried for 24 hours, so that 1.46g of polymer with certain elasticity is obtained. The catalytic efficiency of the catalytic system was 146kg mol-1Ni, weight average molecular weight Mw of the polymer measured at the end of the reaction was 13.27 ten thousand, and molecular weight distribution Mw/Mn was 1.84.
Compared with the comparative example 1, the chain transfer agent is introduced in the examples 1-4, so that the molecular weight of the polymer can be greatly regulated and controlled; compared with comparative examples 2 and 3, when the metal complex of the invention is used as a main catalyst, the polymerization activity is much higher under the high-temperature polymerization condition, and the nickel metal complex of the invention has better thermal stability.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (14)
1. A catalyst composition for the polymerization of long chain alpha-olefins, the catalyst composition comprising:
a main catalyst, a cocatalyst and a chain transfer agent;
the main catalyst is a complex with a chemical structure shown as a formula (I):
wherein X is halogen; r1-R5The same or different, each independently selected from hydrogen and C1-C20At least one of the hydrocarbon groups of (a);
the cocatalyst is selected from at least one of alkyl aluminoxane, aryl boron and borate;
the chain transfer agent is selected from trialkyl aluminum and/or dialkyl zinc.
2. The catalyst composition for the polymerization of long chain α -olefins according to claim 1, wherein in formula (I), R is1-R5Each independently selected from hydrogen and C1-C13At least one of the hydrocarbon groups of (1).
3. The catalyst composition for polymerization of long chain α -olefins according to claim 2, wherein in formula (I), R is1-R5Each independently selected from hydrogen, methyl, ethyl, ethenyl, isopropyl, propenyl, phenyl and C7-C13At least one of aralkyl groups of (a).
4. The catalyst composition for the polymerization of long chain alpha-olefins according to claim 1 wherein the complex is selected from at least one of the following compounds:
1) a complex of formula (I), wherein R1＝R3＝R5＝H，R2＝R4＝Me，X＝Br；
2) A complex of formula (I), wherein R1＝R3＝R2＝R4＝Me，R5＝H，X＝Br；
3) A complex of formula (I), wherein R1＝R3＝R5＝H，R2＝R4＝iPr，X＝Br；
4) A complex of formula (I), wherein R1＝R3＝R5＝H，R2＝R4＝CHPh2，X＝Br；
5) A complex of formula (I), wherein R1＝R3＝H，R2＝R4＝R5＝CHPh2，X＝Br；
6) A complex of formula (I), wherein R1＝R3＝R2＝R4＝R5＝CHPh2，X＝Br；
7) A complex of formula (I), wherein R1＝R3＝R5＝H，R2＝R4＝Me，X＝Cl；
8) A complex of formula (I), wherein R1＝R3＝R2＝R4＝Me，R5＝H，X＝Cl；
9) A complex of formula (I), wherein R1＝R3＝R5＝H，R2＝R4＝iPr，X＝Cl；
10) A complex of formula (I), wherein R1＝R3＝R5＝H，R2＝R4＝CHPh2，X＝Cl；
11) A complex of formula (I), wherein R1＝R3＝H，R2＝R4＝R5＝CHPh2，X＝Cl；
12) A complex of formula (I), wherein R1＝R3＝R2＝R4＝R5＝CHPh2，X＝Cl。
5. The catalyst composition for the polymerization of long chain alpha-olefins according to claim 1, wherein the alkylaluminoxane is methylaluminoxane and/or modified methylaluminoxane; the aryl boron is phenyl boron; the borate is N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.
6. The catalyst composition for the polymerization of long chain alpha olefins according to claim 1 wherein the arylboronic acid is tris (pentafluorophenyl) boron.
7. The catalyst composition for the polymerization of long chain alpha-olefins according to claim 1 wherein the chain transfer agent is selected from at least one of trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, dimethylzinc and diethylzinc.
8. The catalyst composition for the polymerization of long chain alpha-olefins according to claim 1 wherein the molar ratio of aluminum in the cocatalyst to nickel in the procatalyst is (10-10000): 1; or the molar ratio of boron in the cocatalyst to nickel in the main catalyst is (1-500): 1.
9. The catalyst composition for the polymerization of long chain alpha olefins according to claim 1, wherein the molar ratio of aluminum in the chain transfer agent to nickel in the procatalyst is (1-1000): 1; or the molar ratio of the zinc in the chain transfer agent to the nickel in the main catalyst is (1-1000): 1.
10. A process for the polymerization of long chain alpha olefins catalysed by the catalyst composition according to any one of claims 1 to 9, characterized in that the process comprises: in the presence of inert gas, the long-chain alpha-olefin, the main catalyst, the cocatalyst and the chain transfer agent are contacted to carry out polymerization reaction.
11. The process of claim 10, wherein the polymerization reaction is at a temperature of-78 ℃ to 200 ℃.
12. The process of claim 11, wherein the polymerization reaction is at a temperature of-20 ℃ to 150 ℃.
13. The method of claim 10, wherein the amount of the procatalyst is 0.0001 to 10 mmol/L.
14. The method of claim 13, wherein the amount of the procatalyst is 0.001-1 mmol/L.
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| CN105294778A (en) * | 2015-10-14 | 2016-02-03 | 中山大学 | Nickel base complex, and preparation method and application thereof |
| CN105646598A (en) * | 2014-11-17 | 2016-06-08 | 中国科学院化学研究所 | Naphthyl-substituted asymmetric acenaphthenediimine nickel complexes, and preparing method and applications thereof |
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| CN105646598A (en) * | 2014-11-17 | 2016-06-08 | 中国科学院化学研究所 | Naphthyl-substituted asymmetric acenaphthenediimine nickel complexes, and preparing method and applications thereof |
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